CN116422319A - Cerium single-atom nano-enzyme, preparation method thereof and marine antifouling application - Google Patents
Cerium single-atom nano-enzyme, preparation method thereof and marine antifouling application Download PDFInfo
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- CN116422319A CN116422319A CN202310394232.9A CN202310394232A CN116422319A CN 116422319 A CN116422319 A CN 116422319A CN 202310394232 A CN202310394232 A CN 202310394232A CN 116422319 A CN116422319 A CN 116422319A
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- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 230000003373 anti-fouling effect Effects 0.000 title abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 15
- 239000010941 cobalt Substances 0.000 claims abstract description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000000703 Cerium Chemical class 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- -1 cobalt nitride Chemical class 0.000 claims description 4
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 claims description 3
- 229960001759 cerium oxalate Drugs 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- BTVVNGIPFPKDHO-UHFFFAOYSA-K cerium(3+);octadecanoate Chemical compound [Ce+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O BTVVNGIPFPKDHO-UHFFFAOYSA-K 0.000 claims description 3
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 claims description 3
- PHSMPGGNMIPKTH-UHFFFAOYSA-K cerium(3+);trifluoromethanesulfonate Chemical compound [Ce+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F PHSMPGGNMIPKTH-UHFFFAOYSA-K 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- QVYIMIJFGKEJDW-UHFFFAOYSA-N cobalt(ii) selenide Chemical compound [Se]=[Co] QVYIMIJFGKEJDW-UHFFFAOYSA-N 0.000 claims description 3
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 2
- 239000012498 ultrapure water Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 15
- 108090000790 Enzymes Proteins 0.000 abstract description 7
- 102000004190 Enzymes Human genes 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 241000195493 Cryptophyta Species 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- BELBBZDIHDAJOR-UHFFFAOYSA-N Phenolsulfonephthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2S(=O)(=O)O1 BELBBZDIHDAJOR-UHFFFAOYSA-N 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000006911 enzymatic reaction Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229960003531 phenolsulfonphthalein Drugs 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 108010073997 Bromide peroxidase Proteins 0.000 description 1
- 241000238586 Cirripedia Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 102000005741 Metalloproteases Human genes 0.000 description 1
- 108010006035 Metalloproteases Proteins 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- 206010039509 Scab Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 101710143559 Vanadium-dependent bromoperoxidase Proteins 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000008260 defense mechanism Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000001617 migratory effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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Abstract
The invention discloses a preparation method of cerium single-atom nano-enzyme, which comprises the steps of dispersing a certain amount of cobalt-based metal compound in a solvent, dropwise adding cerium salt with a certain concentration into the dispersion liquid, uniformly stirring, and treating by a mixture system to obtain the cerium single-atom nano-enzyme. The cerium single-atom nano-enzyme prepared by the method is firmly anchored on a substrate in a unit point state by utilizing metal cerium, so that the atom utilization rate is maximized, more unsaturated coordination nonmetallic bonds exist in a substrate compound due to the introduction of single atoms, and the edges of the substrate are exposed with more abundant active sites, thereby accelerating the catalytic reaction kinetics of the enzyme and finally improving the marine biofouling resistance of the enzyme. The method is simple and easy to produce in large scale, and provides a new idea for preparing novel environment-friendly, low-cost and efficient marine antifouling materials.
Description
Technical Field
The invention relates to the field of marine antifouling nanometer materials, in particular to cerium single-atom nanometer enzyme, a preparation method thereof and marine antifouling application.
Background
Marine biofouling refers to the attachment and growth of organisms such as bacteria, algae, crusts (e.g., shells, barnacles) on wet surfaces, and any surface immersed in the ocean is affected by marine biofouling. The traditional antifouling coating material is gradually forbidden by countries around the world due to the toxic substances, so that the development of a novel green and efficient antifouling coating material becomes a great technical problem facing the surface protection of equipment.
According to the current literature reports, certain algae in the ocean have evolved natural fouling defense mechanisms, and certain algae can utilize the autonomously secreted vanadium haloperoxidase to catalyze halogen ions in the sea water into hypohalous acid with antibacterial and biofilm adhesion resisting effects, so that the aim of resisting biofouling is fulfilled. However, the natural enzyme has the problems of high extraction cost, easy degradation, harsh acquisition conditions and the like.
Monoatomic nanoenzyme is a nanoenzyme of atomic fraction dispersed active sites, which is more similar to metalloprotease, has the advantages of common nanoenzyme, and has higher catalytic activity. Because monoatomic nanoenzymes have definite atomic-level metal dispersibility and unique electronic/geometric structures, higher atom utilization rate and rich active sites, the monoatomic nanoenzymes are used for simulating protease in bionic chemistry in recent years, but the traditional nanoenzymes still face great challenges of uneven element composition, low active site density, complex catalytic mechanism and the like.
Therefore, it is necessary to develop a new, environmentally friendly, low cost and efficient marine antifouling material.
Disclosure of Invention
In view of the above, the invention provides a preparation method of cerium single-atom nano-enzyme, which solves the problems existing in the prior art.
The invention provides a preparation method of cerium single-atom nano-enzyme, which comprises the following steps: firstly dispersing a certain amount of cobalt-based metal compound in a solvent, then dropwise adding cerium salt with a certain concentration into the dispersion liquid, uniformly stirring, and then treating by a mixture system to obtain the cerium single-atom nano-enzyme.
Preferably, the metal compound is selected from one of cobalt phosphide, cobalt oxide, cobalt sulfide, cobalt selenide and cobalt nitride.
Preferably, the cerium salt is selected from one of cerium oxalate, cerium chloride, cerium nitrate, cerium ammonium nitrate, cerium triflate and cerium stearate.
Preferably, the mass of the cobalt-based metal compound is 100-500mg.
Preferably, the cerium salt is present in a volume of 2-9mL and at a concentration of 0.05-2mM.
Preferably, the mixture system is treated by hydrothermal growth at 130 ℃ for 10 hours.
In another aspect, the invention provides a cerium single-atom nano-enzyme and application thereof in preparing marine anti-biofouling materials.
The preparation method of the cerium single-atom nano-enzyme provided by the invention has the advantages of simple steps, low cost and mass production. The cerium single-atom nano enzyme prepared by the method is firmly anchored on the substrate in a unit point state by utilizing the metal cerium, so that the atom utilization rate is maximized, more unsaturated coordination nonmetallic bonds exist in the substrate compound due to the introduction of single atoms, and the edges of the substrate are exposed to richer active sites, thereby accelerating the catalysis reaction kinetics of the enzyme-like enzyme and finally exhibiting excellent marine biofouling resistance.
Further, compared with the prior anti-fouling technology, the cerium single-atom nano-enzyme prepared by the technical scheme of the invention is clean and environment-friendly, and does not have the problem of secondary pollution of toxic marine ecosystems.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) picture of cerium single-atom nanoenzyme prepared by the method of example one;
FIG. 2 is a Transmission Electron Microscope (TEM) image of cerium monoatomic nanoenzyme prepared by the method of example one;
FIG. 3 is a scanning transmission electron microscope (HADDF) picture of cerium monoatomic nanoenzyme prepared using the method of example one;
FIG. 4 is a scanning transmission electron microscope (HADDF) image of cerium monoatomic nanoenzyme prepared using the method of example one;
FIG. 5 is a graph showing the enzymatic reaction kinetics of cerium single-atom nanoenzymes prepared by the method of example one, respectively, catalyzing phenol red bromination, wherein (a) is performed according to Br - A curve made by the change in concentration, (b) according to H 2 O 2 Curves made with changes in concentration;
FIG. 6 shows the cerium single-atom nano-enzyme prepared by the method of example one in H 2 O 2 And Br (Br) - Incubating a control picture of E.coli in the presence;
fig. 7 is a photograph of a cerium single-atom nano-enzyme prepared by the method of example one hung plate for 92 days in a real marine environment.
Detailed Description
The principles and features of the present invention are described below with reference to the drawings, the illustrated embodiments are provided for illustration only and are not intended to limit the scope of the present invention.
Embodiment one: the preparation method of the cerium single-atom nano-enzyme comprises the following steps:
dispersing 300mg of cobalt phosphide in 200mL of ultrapure water by ultrasonic, dropwise adding 4mL of ammonium cerium nitrate solution with the concentration of 0.5mM into the dispersion by using a syringe pump, stirring for 5h, centrifuging, washing, transferring to a 50mL hydrothermal kettle, reacting for 10h at 130 ℃, and finally centrifuging and drying to obtain the cerium single-atom nano-enzyme.
(1) The cerium single-atom nano-enzyme prepared in the embodiment is tested and characterized by using a scanning electron microscope and a transmission electron microscope respectively, and as can be seen from the results of fig. 1 and 2, the cerium single-atom nano-enzyme prepared in the embodiment has a two-dimensional nano-sheet structure, and no cerium-related nano-particles or clusters are observed on the nano-sheet.
(2) The cerium monoatomic nano-enzyme prepared in this example was tested by using a spherical aberration electron microscope, and as can be seen from the result of fig. 3, cerium was distributed on the carrier in the form of isolated atoms with a size of less than 1 nm, and no clusters or particles related to cerium species were present on the carrier, indicating successful preparation of cerium monoatomic nano-enzyme.
(3) The cerium single-atom nano-enzyme prepared in the embodiment is tested by utilizing the characterization of X-ray diffraction, and as shown in fig. 4, the cerium single-atom nano-enzyme in the embodiment has the same diffraction peak as a pure cobalt phosphide substrate, and no other peak appears, so that the cerium atoms have a small load on the substrate and have an extremely small particle size.
(4) Cerium single-atom nano-enzyme prepared in this example is in H 2 O 2 And when the bromine source is coexistent, taking phenol red as a color developing agent, and observing an enzymatic reaction dynamic curve. When respectively changing H 2 O 2 Or bromine source, other substrate concentrations remain constant. The results from fig. 5 show that: cerium single-atom nano-enzyme pair H prepared in this example 2 O 2 And Br (Br) - Exhibit typical migratory behavior. The two reciprocal plots of the linear weaver-Burk were plotted to obtain the Mie constant (K) for the nanoenzyme to simulate the haloperoxidase-catalyzed process m ) Cerium single-atom nano-enzyme pair H prepared in this example 2 O 2 Lower K of substrate m Value (221.9. Mu.M) indicating that it is against H 2 O 2 Stronger binding affinity.
(5) The cerium single-atom nano-enzyme prepared in the embodiment is used in H 2 O 2 And Br (Br) - Incubation with diluted bacterial solution for 12h in the presence of the bacteria solution was found by comparing the results in fig. 6: the colony number on the culture medium substrate coated by the cerium single-atom nano-enzyme is obviously lower than that of the base material, which shows that the cerium nano-enzyme catalyzes Br - The HOBr generated by oxidation can effectively inhibit the growth and propagation of bacterial biofilms.
(7) The cerium single-atom nano-enzyme of the present example was uniformly mixed with a commercial ship paint according to a weight ratio of 5% and coated on a stainless steel plate, and hung in a real marine environment for 52 days, as found by comparison of the results of fig. 7: compared with the pure substrate material (a), the fouling condition of the steel plate (b) treated by the cerium single-atom nano-enzyme is greatly reduced, and the cerium single-atom nano-enzyme has good marine biofouling prevention property.
In another embodiment, the metal compound is selected from one of cobalt phosphide, cobalt oxide, cobalt selenide, and cobalt nitride.
In another embodiment, the cerium salt is selected from one of cerium oxalate, cerium chloride, cerium nitrate, cerium triflate, and cerium stearate.
In another embodiment, the mass of the cobalt-based metal compound is 100-500mg.
In another embodiment, the cerium salt is present in a volume of 2-9mL and a concentration of 0.05-2mM.
In conclusion, the cerium single-atom nano-enzyme prepared by the method provided by the invention has the advantages that the metal cerium is firmly anchored on the substrate in a unit point state, so that the atom utilization rate is maximized, more unsaturated coordination nonmetallic bonds exist in the substrate compound due to the introduction of single atoms, and the edges of the substrate expose more abundant active sites, so that the kinetics of the enzyme catalytic reaction is accelerated. Further, the cerium single-atom nano-enzyme prepared by the invention simulates vanadium bromoperoxidase, and is characterized in that H 2 O 2 Can effectively catalyze Br in the presence of oxidant - HOBr is generated, so that signal molecules in bacteria are halogenated and inactivated, communication among cells is inhibited, and adhesion of microorganisms is effectively prevented. Furthermore, the cerium single-atom nano-enzyme prepared by the method disclosed by the invention has good marine biofouling prevention property.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather to enable any modification, equivalent replacement, improvement or the like to be made within the spirit and principles of the invention.
Claims (9)
1. The preparation method of the cerium single-atom nano-enzyme is characterized by comprising the following steps of: firstly dispersing a certain amount of cobalt-based metal compound in a solvent, then dropwise adding cerium salt with a certain concentration into the dispersion liquid, uniformly stirring, and then treating by a mixture system to obtain the cerium single-atom nano-enzyme.
2. The method for preparing cerium single-atom nano-enzyme according to claim 1, which is characterized in that: the metal compound is selected from one of cobalt phosphide, cobalt oxide, cobalt sulfide, cobalt selenide and cobalt nitride.
3. The method for preparing cerium single-atom nano-enzyme according to claim 1, which is characterized in that: the cerium salt is selected from one of cerium oxalate, cerium chloride, cerium nitrate, ammonium cerium nitrate, cerium triflate and cerium stearate.
4. The method for preparing cerium single-atom nano-enzyme according to claim 1, which is characterized in that: the mass of the cobalt-based metal compound is 100-500mg.
5. The method for preparing cerium single-atom nano-enzyme according to claim 1, which is characterized in that: the cerium salt has a volume of 2-9mL and a concentration of 0.05-2mM.
6. The method for preparing cerium single-atom nano-enzyme according to claim 1, which is characterized in that: the mixture system was treated to be grown hydrothermally at 130 ℃ for 10h.
7. The method for preparing cerium single-atom nano-enzyme according to claim 1, which is characterized by comprising the following steps: and (3) dispersing 300mg of cobalt phosphide in 200mL of ultrapure water by ultrasonic, dropwise adding 4mL of ammonium cerium nitrate solution with the concentration of 0.5mM into the dispersion liquid by using a syringe pump, stirring for 5h, centrifugally washing, transferring to a 50mL hydrothermal kettle, carrying out hydrothermal reaction for 10h at 130 ℃, and centrifugally drying to obtain the cerium monoatomic nano-enzyme.
8. A cerium monoatomic nanoenzyme prepared according to the method of any one of claims 1 to 7.
9. The use of the cerium single-atom nano-enzyme according to claim 8 for preparing marine anti-biofouling materials.
Priority Applications (1)
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| CN117186770A (en) * | 2023-11-02 | 2023-12-08 | 天津永续新材料有限公司 | Antifouling coating of nano enzyme synergistic biomass material, preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117186770A (en) * | 2023-11-02 | 2023-12-08 | 天津永续新材料有限公司 | Antifouling coating of nano enzyme synergistic biomass material, preparation method and application |
| CN117186770B (en) * | 2023-11-02 | 2024-04-12 | 天津永续新材料有限公司 | Antifouling coating of nano enzyme synergistic biomass material, preparation method and application |
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